This application is based on application Numbers 98-20829 and 99-18840 filed in the Korean Industrial Property Office on Jun. 5, 1998 and May 25, 1999 respectively the content of which is incorporated hereinto by reference.
(a) Field of the Invention
The present invention relates to a bleaching activator and a bleaching composition comprising the same, particularly to a bleaching activator comprising a phenanthroline manganese complex and a bleaching composition comprising the same.
(b) Description of the Related Art
Inorganic peroxide (which generates hydrogen peroxide (H2O2) when dissolved in water) such as sodium perborate (NaBO3.H2O, NaBO3.4H2O) and sodium percarbonate (2Na2CO3.3H2O2), and hydrogen peroxide have been used as an oxidant for sterilizing or bleaching for a long time. The oxidizing power of these compounds in a dilute solution, that is, the bleaching power, is greatly depended on the temperature. For example, sufficient bleaching effects are obtained only after reaching a temperature of more than 80xc2x0 C. when using sodium perborate or 60xc2x0 C. when sodium percarbonate for bleaching textile soiled by fruit juice, wine, vegetables, coffee, or tea. Although the bleaching power of inorganic peroxide radically decreases at a temperature less than 60xc2x0 C., this peroxide oxidizing power at a low temperature can be elevated by adding a material called a bleaching activator. Varieties of compounds of this material have been suggested in literature, and examples include acyl compounds such as tetraacetylethylenediamine (TAED), ester compounds such as nonanoyloxybenzenesulfonate (NOBS) and isononanoyloxybenzenesulfonate (ISONOBS), etc. Effects generated at 95xc2x0 C. by peroxide alone can be generated at 60xc2x0 C. if these materials are added. However, it is well known that at a temperature lower than 60xc2x0 C. the activator effect is reduced drastically.
As there is a decreasing trend in washing and cleansing temperatures worldwide due to environmental protection and energy conservation, there is interest in the development of bleaching activators that can exhibit bleaching power at even low temperatures. Many transition metal ions are known to promote the decomposition of hydrogen peroxide (H2O2) or peroxide, so the use of transition metal salts has been suggested. However, a direct application of transition metal salts undesirably causes a bleaching agent to decomposed. Therefore, varieties of transition metal complexes have been developed for the purpose of a bleaching activation, and some of them have been used practically. These complex compounds should not decomposed drastically and should be stable during hydrolysis, oxidation, reduction, etc., so that the transition metal complexes can be used effectively as a bleaching catalyst.
Although a considerable large number of complex compounds (employing transition metals such as cobalt (Co), manganese (Mn), iron (Fe), etc.) have been developed recently, the use of cobalt is not desirable for environmental reasons. Therefore, a lot of patents have been recording the use of manganese. However, as manganese ions or many manganese complex compounds are very much unstable during hydrolysis, these compounds are not adequate to be used with inorganic peroxide bleaching agents.
It is recorded in European Laid-open Patent Numbers 458,397 B1 and 458,398 B1 that binuclear manganese complexes synthesized using a ligand of 1,4,7-trimethyl-1,4,7-triazacyclononane have a considerably high degree of activation in promoting the bleaching effect of peroxides even at the low temperature. However, there is a problem in that various steps must be used to synthesize this ligand, resulting in increasing the overall price of the ligand.
It is an object of the present invention to provide a bleaching activator comprising manganese complexes improving the bleaching activation of peroxide which is a hydrogen peroxide generating oxygen based bleaching agent considering the above mentioned problems of conventional technologies.
It is an other object of the present invention to provide a bleaching activator which is granulated, oil coated, or capsulated, and that increases the stability of the above manganese complex bleaching activators.
It is an another object of the present invention to provide a bleaching composition comprising the above manganese complex bleaching activators.
It is an another object of the present invention to provide a bleaching activator and a bleaching composition comprising the same that increase a bleaching power of bleaching agents used in laundry, dish washing, false teeth rinsing, and in industries such as fabrics, paper, and pulp.
It is an another object of the present invention to provide a bleaching agent and a bleaching detergent composition that are useful in an environment where a low temperature washing is prevalent, such as in Korea.
In order to accomplish the above objects, the present invention provides a bleaching activator increasing the bleaching power of sodium percarbonate or sodium perborate, wherein the bleaching activator having a phenanthroline manganese complex comprising one or more compounds selected from a group including [MnCl2(phen)2], [MnBr2(phen)2], [Mn(H2O)2(phen)2](SO4), [Mn(H2O)2(phen)2](ClO4)2, [Mn(CH3COO)2(phen)2], [MnIIICl3(H2O)(phen)], [(phen)2MnIV(xcexc-O)2MnIV(phen)2](ClO4)4.H2O, [(phen)2MnIII(xcexc-O)2MnIV(phen)2](ClO4)3.xH2O (where x=2 or 4), and [(phen)(H2O)MnIII(xcexc-O)(xcexc-CH3COO)2MnIII(phen)(H2O)](PF6)2.
The above phenanthroline manganese complex can be used itself, but is preferably used in a granulated, oil coated, or capsulated form.
The above granulated bleaching activator is manufactured by mixing a) 100 to 1000 weight parts of binder; b) 110 to 3000 weight parts of filler; and c) 100 to 1000 weight parts of a mixed solution of the above phenanthroline manganese complex compound powder and a photo-bleaching agent solution (comprising 0.1 to 20 wt % of photo-bleaching agent).
The above oil coated bleaching activator is manufactured by coating phenanthroline manganese complex granules with oil in water emulsion composition.
The above capsulated bleaching activator is manufactured by coating 1000 weight parts of oil coated phenanthroline manganese complex granules with 100 to 3000 weight parts of a mixture of water soluble materials, photo-bleaching agent or fluorescent dye.
Furthermore, the present invention provides a bleaching composition comprising a bleaching activator comprising the above phenanthroline manganese complex.
Particularly, the above bleaching composition is a peroxide bleaching agent comprising:
a) 0.001 to 5 wt % of a bleaching activator comprising the above manganese based phenanthroline manganese complex; and
b) 1 to 99 wt % of sodium percarbonate peroxide or sodium perbonate peroxide,
xe2x80x83or a bleaching detergent comprising:
a) 1 to 40 wt % of peroxide;
b) 1 to 50 wt % of anion surfactant;
c) 1 to 50 wt % of non ion surfactant;
d) 1 to 70 wt % of builder;
e) 0.1 to 10 wt % of tetraacetylethyleneamine; and
f) 0.0001 to 0.5 wt % of bleaching activator comprising the above manganese based phenanthroline manganese complex,
xe2x80x83or, the above bleaching composition is a false teeth rinsing agent comprising:
a) 1 to 70 wt % of peroxide comprising one or more selected from a group composed of urea peroxide, sodium percarbonate, sodium perbonate, and calcium peroxide;
b) 0.001 to 10 wt % of bleaching activator comprising the above manganese based phenanthroline manganese complex; and
c) additives comprising a bubbling agent, wetting agent, viscosity increasing agent, and abradant.
And the above bleaching activator comprising a phenanthroline manganese complex compound is granulated, oil coated, or capsulated phenanthroline manganese complex.
The present invention is described in detail as follows:
The inventors of the present invention found that a series of phenanthroline manganese complexes could explicitly promote the effects of a bleaching agent peroxide using a relatively inexpensive ligand such as phenanthroline (1,10-phenanthroline; abbreviated as phen). These phenanthroline manganese complexes are relatively easily synthesized, quite stable in hydrolysis, oxidation, reduction, etc., and have excellent performance compared to their price.
The above manganese complexes are stable even in a basic solution and they are catalysts which activate the peroxide bleaching effect on red wine or coffee, etc., even at a low temperature. Therefore, the present invention is characterized in that during the bleaching or cleansing using a bleaching agent such as a hydrogen peroxide generating inorganic peroxide, peroxy-acid, and its salt, the bleaching agent becomes activated by the above listed compounds with small amounts of bleaching agent added.
Generally, bleaching agent is a solid phase, used by being dissolved in water, with this bleaching agent""s aqueous solution being most effective in the pH range of 8 to 11. The effective amount of manganese complex is generally indicated in the amount of manganese in an aqueous solution of bleaching agent, generally being in the range of 0.001 to 50 ppm. High concentrated contents can be used in the industrial processes such as the bleaching fabric, paper, and pulp, and a small amount can be used in laundry or dish washing and the rinsing of a false teeth.
Another characteristic of the present invention is to provide a bleaching agent composition comprising a manganese based content of 0.0001 to 5 wt % (preferably 0.001 to 1 wt %) as a catalyst for activating a 1 to 99 wt % of peroxide and one of the above listed phenanthroline manganese complex compounds. At this time, additives such as surfactant, zeolite, sodium carbonate, sodium sulfate, enzyme, fragrance, etc., can be added depending on the situation for a prevention of recontamination, all types of stability, and bleaching agent performance.
Supplying sources generating a hydrogen peroxide includes inorganic peroxides such as alkali metal perborate, percarbonate, perphosphate, and persulfate, organic peroxides such as urea peroxide, and alkali metal peroxides. Particularly, bleaching materials suitable for washing are sodium percarbonate, sodium perborate monohydrate, and sodium perborate tetrahydrate. Sodium perborate monohydrate is preferable as it has more superior storage stability and is dissolved more quickly than sodium perborate tetrahydrate. Although sodium percarbonate has an advantage in its environment friendly aspects, its stability is lower than that of sodium perborate. For the purpose of bleaching, two or more of these compounds can be mixed and used. Furthermore, these bleaching agents can be used along with peroxy-acid bleaching agent precursor, the use of precursor not only increases bleaching effect, but also has a disinfection effect resulting in hygienic advantages. Organic peroxy-acid can also be used as a peroxide.
One of characteristics of the present invention is to provide a bleaching detergent composition comprising of one of the phenanthroline manganese complexes such as peroxide, anion surfactant, non ionic surfactant, one or more of builders, tetraacetylethyleneamine (TAED), and a bleaching activation catalyst.
A bleaching detergent composition in the present invention comprises 1 to 50 wt % (preferably 5 to 35 wt %) of peroxide. It can also comprise a 0.1 to 25 wt % (preferably 1 to 10 wt %) of tetraacetylethylenediamine (TAED). In the case where it comprises a phenanthroline manganese complex, 0.0001 to 0.5 wt % (preferably 0.001 to 0.3 wt %) of manganese content out of a detergent composition can be mixed.
An anionic or non ionic surfactant can be used as the above surfactant. Total content of surfactant is 1 to 50 wt % (preferably 10 to 40 wt %) of composition. One or more compounds selected from alkylbenzene sulfonates, fatty acid salts, alkane monosulfonates, and olefinsulfonates can be used as an anionic surfactant, and one or more compounds selected from oxo-alcohol polyethyleneglycolethers, fatty acid alkanol amides, and ethoxylated alkanes can be used as a non ionic surfactant.
Materials used as a builder include alkalimetal polyphosphates such as sodium tripolyphosphates, alumino silicates such as zeolites, polyacetalcarboxylates, polycarboxylates, etc. A 1 to 70 wt % (preferably 10 to 40 wt %) of builder is used.
Besides the above materials, a bleaching detergent composition of the present invention can use inorganic salts such as sodium carbonate, sodium sulfate, etc., which generally can be used as a powder detergent, and polymers as additives to lower water hardness and prevent recontamination. Furthermore, additives such as fluorescent agent, enzymes, and fragrance can be used to increase the performance of a detergent.
The another characteristics of the present invention is to provide a composition of a false teeth rinsing agent comprising one or more items selected from a group including generally used peroxide, a bubbling agent, wetting agent, viscosity increasing agent, abradant, and the above phenanthroline manganese complex.
The above composition of a false teeth rinsing agent uses 0.01 to 70 wt % (preferably 0.1 to 30 wt %) of peroxide (hydrogen peroxide/total of rinsing agent) comprising one or more compounds selected from a group composed of urea peroxide, sodium percarbonate, sodium perborate, and calcium peroxide. 0.001 to 10 wt % (preferably 0.005 to 7 wt %) of a phenanthroline manganese complex (manganese content/total composition of a false teeth rinsing agent) can be used.
Peroxides and bleaching activators used in the present invention are solid particles, and can be used in a detergent in a powder or granule type form manufactured by already known technologies. It can be manufactured by adding peroxides and phenanthroline manganese complex to powder detergent manufactured using processes of spray drying, non-tower type, extrusion, granulation, and concentration.
The another characteristics of the present invention is to provide conditions of granulization, oil coating, and capsulation to increase the stability of the bleaching activator""s product. A phenanthroline manganese complex powder is preferably used as a bleaching activator. Manganese salts are replaced with phenanthroline among ethyl alcohol, phenanthroline manganese complex (which is not dissolved by ethyl alcohol) is separated, the excess amount of non reacted materials is removed by cleaning with ethyl alcohol, then it is dried and crushed turning the phenanthroline manganese complex into powder. A phenanthroline manganese complex manufactured as per this method is preferrably used by separating the peroxide bleaching agent and other constituents. It is accomplished through the granulation, oil coating, and capsulation processes of compound.
In granulation, granules similar to spheres can be manufactured using Lxc3x6dige mixer or extruder, binder comprising one or more items selected from sugar, sodium silicate, polyethyleneglycol, fatty acid salts, hydroxypropylmethylcellulose, cellulose, Arabic gum, ethyleneoxide based non ionic surfactant, and polyvinylpyrrolidone can be used, the filler, which is mixed with the binder, includes one or more out of Zeolite 4A, X, Y, L, P, omega, zeolone modernite, ZSM-5, F, W, ethylenediamine tetraacetic acid (EDTA), and sodium ethylenediaminetetraacetate. At this time, photo-bleaching agents should be used along with binders and fillers to prevent color changes caused by metal oxidation. Any photo-bleaching agents that are normally used in the technology fields of the present invention can be used.
In performing the granulation process, after 1000 wt parts of filler, 100 to 1000 wt parts (preferably 200 to 600 wt parts) of binder, and 100 to 1000 wt parts (preferably 100 to 500 wt parts) of powder type complex were first put into a Lxc3x6dige mixer, premixing is performed. When compounds of filler and binder have been uniformly mixed, with only a main blade operated, a top lid of the mixer was opened, and 100 to 1000 wt parts (preferably 100 to 500 wt parts) of photo-bleaching solution (0.1 to 20 wt % (preferably 0.1 to 10 wt %) of photo-bleaching agent per total weight of solution is used) was added, the lid was then closed, and the cross screw operated. When particles are grown to the appropriate sizes, 100 to 2000 wt parts (preferably 200 to 1000 wt parts) of fillers are put into one to 5 times completing the granulation. Therefore, total amount of fillers used is 1100 to 3000 wt parts, and the size of the final granules manufactured according to this method 100 to 3000 xcexcm, preferably 200 to 2000 xcexcm.
Stabilization of the moisture content of granuled bleaching activators can be increased by forming a hydrophobic layer of thin oil coating before capsulation. Oil coating is made using oil in water emulsion, oil in water emulsion is composed of 5 to 50 wt parts of oil and 50 to 95 wt parts of water. Oil can be used comprising one or more substances selected from a group including silicone oil with a viscosity of 100 to 5,000 centistokes (cst), a mixture of 70 to 90 wt % silicone oil with a viscosity of 100 to 5,000 cst and silicone oil with a viscosity of 10,000 to 100,000 cst, a mixture of 95 to 99.5 wt % silicone oil with a viscosity of 100 to 5,000 cst and 0.1 to 5 wt % wax, liquid paraffin, soybean oil, olive oil, and sesame oil. Oil in water emulsion comprises 0.5 to 30 wt % of emulsifiers, with typical emulsifiers including soap or polyoxyethylenesorbitan monostearates.
In the oil coating performing process, 1000 wt parts of granules are put into fluidized bed, with the equipment operated, 20 to 1000 wt parts (preferably 20 to 500 wt parts) of coating materials are sprayed through a spray nozzle at an upper or a lower part of a container fuidizing the granules with hot air. Hot air temperature inside the fluidized bed is maintained between 60xc2x0 C. to 200xc2x0 C., and preferably between 60xc2x0 C. to 100xc2x0 C.
The oil coated bleaching activator granules can be capsulated continuously in the same fluidized bed. Capsulation is performed using water soluble materials combined with photo-bleaching agent and/or fluorescent whitening agents. Usable water soluble materials that can be used are one or more items selected from a group including albumin, gelatin, Arabic gum, agaroses, alginates, cellulose, celluloseacetatephthalates, methylcelluloses, ethylcelluloses, hydroxypropylcelluloses, polyvinylalcohols, polyvinylpyrrolidones, silicone polymers, soluble starches, dextrins, fatty acid salts, fatty acids, fatty alcohols, chitosan, and a photo-bleaching agent and fluorescent dyes capable of being mixed with water soluble materials and which are commonly employed in the technology fields of the present invention. A photo-bleaching agent is preferably Timolux DBS of CIBA Corporation, fluorescent dyes preferably include Tinopal CBS-X(disodium-4,4xe2x80x2-bis(2-sulfostyryl) biphenyl; CIBA) or CBW (disodium- 4,4xe2x80x2-bis{[4-anilino-6-(N-ethyl-N-2-hydroxyethyl)amino-1,3,5-triazin-2-yl]amino}stilbene-2,2xe2x80x2-disulfonate; Kyung-in Synthetics Corporation). An aqueous solution having the concentrations of 2 to 50 wt % (preferably 5 to 30 wt %) of water soluble material, 0.1 to 20 wt % (preferably 0.1 to 10 wt %) of photo-bleaching agent, and 1 to 50 wt % (preferably 1 to 30 wt %) of fluorescent dye are manufactured and used. Either a photo-bleaching agent and/or fluorescent dye can be used.
A capsulation process can be performed by putting 1000 wt parts of oil coated granules into a fluidized bed. The granules are fluidized by hot air with the fluidized bed operation, and 100 to 3000 wt parts (preferably 100 to 2000 wt parts) of capsulated material, i.e., an aqueous solution comprising water soluble material combined with a photo-bleaching agent and/or fluorescent dye is sprayed through a spray nozzle at side or lower part of container. Hot air is maintained at a temperature of between 50xc2x0 C. to 200xc2x0 C., preferably between 50xc2x0 C. to 100xc2x0 C., the size of capsulated bleaching activator manufactured according to this is controlled to be within the range of 200 to 4000 xcexcm, preferably 300 to 3000 xcexcm. The size of capsulated bleaching activator can be controlled depending on the amount of capsulated materials, and reaction conditions such as temperature, spraying rate, flow volume of air, etc. Therefore, by combining these conditions properly, desired sized capsules can be obtained.